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AsFeP0 - A model concept for in situ investigation or arsenic and phosphate adsorption to predefined iron minerals and to characterize transformation processes of iron minerals

Shallow groundwater of the huge deltaic systems of Asia like the Red River Delta in Vietnam is often enriched in inorganic arsenic (As), threatening the health of millions of residents. The massive abstraction of groundwater in these areas locally causes an irreversible mixing of arsenic-free groundwater resources with arsenic-rich groundwater. Increased concentrations of competitive anions, especially phosphate (PO43-), decrease the immobilization capacity of the sediments. During transport, the mobility of dissolved As in local aquifers is strongly influenced by adsorption to sedimentary and ubiquitously occurring iron(oxyhydr)oxides. Additionally, arsenic-rich groundwater is often enriched in reduced iron (Fe2+) as well, which is capable to react with iron(oxyhydr)oxides, thereby inducing mineral transformations. Such transformations permanently affect the arsenic adsorption and immobilization capacity of the sediments.Within the scope of this research project, the underlying mechanisms related to As transport and the resulting threat to arsenic-free groundwater resources will be characterized in cooperation with the Swiss Federal Institute of Aquatic Science and Technology (Eawag). The research concept aims at assessing the complex interactions within the arsenic-iron-phosphate-system under field conditions at a study site next to the Red River. First, filtration experiments using local groundwater enriched in As and PO43- will be used to determine the As adsorption capacity of different and previously geochemically characterized iron(oxyhydr)oxides. In a second step, sample carrier containing As loaded iron(oxyhydr)oxides will be introduced into surface near aquifer parts of the study site (via existing groundwater monitoring wells). These samples will be exposed to local groundwater characterized by increased As, Fe2+ and PO43- concentrations for the following nine months. Using the in situ exposition of predefined iron(oxyhydr)oxides, it will be possible to distinguish potential mineral transformations and their influences on the As immobilization capacity of the respective iron(oxyhydr)oxides. By combining the results and outcomes of the field experiments, new and important conclusions regarding the mobility of As can be drawn. The data can be used to create a hydrochemical transport model describing reactive As transport within the investigation area. In addition, the results of the in situ exposition experiments will allow to draw conclusions in respective to the long term As immobilization capacity of different iron(oxyhydr)oxides, which is an essential information regarding in situ decontamination techniques.

Community-mediated mechanisms to stabilize pollination of agricultural production highly dependent on shrinking honey bee populations under global change

Almond in California represents an agroecosystem pollinated solely by a single species, the European honey bee, a species that is becoming increasingly difficult and expensive to manage due to substantial, unpredictable mortality. Therefore, sustainable and high output production require a more integrated approach that diversifies sources of pollination. For this purpose, detailed data of our understanding how diversity can stabilize pollination are required. The project will identify alternative wild pollinator species and collect high quality data contributing to our understanding of how diversity (pollen and insects) can bolster honey bee pollination during stable and unstable climatic conditions. The research will be carried out on almond orchards in Northern California known to be either pollinator species rich (up to 30 species) or depauperate (honey bees only). The replicated extremes in pollinator diversity represent a unique opportunity to study the effects of diversity on pollination in real agroecosystems combined with laboratory and glasshouse experiments. The overall goal is to provide basic research that is essential for our general understanding of how insect diversity can affect high-quality pollination under land use and climate change.

Biogenic formation of non-extractable residues from pesticides in soil

During microbial turnover of organic chemicals in soil, non-extractable residues (NER) are formed frequently. Studies on NER formation usually performed with radioisotope labelled tracer compounds are limited to localisation and quantitative analyses but their chemical composition is left unknown. Recently, we could show for 2,4-dichlorophenoxyacetic acid and ibuprofen that during microbial turnover in soil nearly all NER were derived from microbial biomass, since degrading bacteria use the pollutant carbon for their biomass synthesis. Their cell debris is subsequently stabilised within soil organic matter (SOM) forming biogenic NER (bioNER). It is still unknown whether bioNER are also formed during biodegradation of other, structurally different compound classes of organic contaminants. Therefore, agricultural soil will be incubated with labelled compounds of five classes of commonly used and emerging pesticides: organophosphate, phenylurea, triazinone, benzothiadiazine and aryloxyphenoxypropionic acid. The fate of the label will be monitored in both living and non-living SOM pools and the formation of bioNER will be quantified for each compound over extended periods of time. In addition, soil samples from long-term lysimeter studies with 14C-labelled pesticide residues (e.g. triazine, benzothiazole and phenoxypropionic acid group) will be also analysed for bioNER formation. The results will be summarised to identify the metabolic conditions of microorganisms needed for bioNER formation and to develop an extended concept of risk assessment including bioNER formation in soils.

Biogenic soil structures: feedbacks between bioactivity and spatial heterogeneity of water storage and fluxes from plot to hillslope scale

Soil structure determines a large part of the spatial heterogeneity in water storage and fluxes from the plot to the hillslope scale. In recent decades important progress in hydrological research has been achieved by including soil structure in hydrological models. One of the main problems herein remains the difficulty of measuring soil structure and quantifying its influence on hydrological processes. As soil structure is very often of biogenic origin (macropores), the main objective of this project is to use the influence of bioactivity and resulting soil structures to describe and support modelling of hydrological processes at different scales. Therefore, local scale bioactivity will be linked to local infiltration patterns under varying catchment conditions. At hillslope scale, the spatial distribution of bioactivity patterns will be linked to connectivity of subsurface structures to explain subsurface stormflow generation. Then we will apply species distribution modelling of key organisms in order to extrapolate the gained knowledge to the catchment scale. As on one hand, bioactivity influences the hydrological processes, but on the other hand the species distribution also depends on soil moisture contents, including the feedbacks between bioactivity and soil hydrology is pivotal for getting reliable predictions of catchment scale hydrological behavior under land use change and climate change.

Diffusion and advection with sorption of anions, cations and non-polar molecules in organo-clays at varying thermo-chemical conditions - validation by analytical methods and molecular simulation

The sorption of anions in geotechnical multibarrier systems of planned high level waste repositories (HLWR) and of non-ionic and organic pollutants in conventional waste disposals are in the center of recent research. In aquatic systems, persistent radionuclides such as 79Se, 99Tc, 129I exist in a form of anions. There is strongly increasing need to find materials with high sorption capacities for such pollutants. Specific requirements on barrier materials are long-term stability of adsorbent under various conditions such as T > 100 C, varying hydrostatic pressure, and the presence of competing ions. Organo-clays are capable to sorb high amounts of cations, anions and non-polar molecules simultaneously having selectivity for certain ions. This project is proposed to improve the understanding of sorption and desorption processes in organo-clays. Additionally, the modification of material properties under varying chemical and thermal conditions will be determined by performing diffusion and advection experiments. Changes by sorption and diffusion will be analyzed by determining surface charge and contact angles. Molecular simulations on models of organo-clays will be conducted in an accord with experiments with aim to understand and analyze experimental results. The computational part of the project will profit from the collaboration of German partner with the group in Vienna, which has a long standing experience in a modeling of clay minerals.

Nachbewilligung zur Dritten Phase des Projektes: Entwicklung eines zweistufigen biologischen Verfahrens zur Reinigung von Deponiesickerwasser und industriellen Abwässern mit komplexen Stoffgemischen

Zielsetzung und Anlass des Vorhabens: Ziel der letzten Projektphase war es, mit einer Langzeit-Praxiserprobung das zweistufige biologische Verfahren zur Deponiesickerwasserreinigung als Stand der Technik zu etablieren und zu bilanzieren. Nach der Inbetriebnahme des Technikums am Deponiestandort Schöneiche ging es in der zwölfmonatigen Laufzeit des Projektes AZ 14996/04 in den Langzeitversuchen um die Validierung der Laborergebnisse im technischen Maßstab, die verfahrenstechnische Optimierung der Anlage und um eine damit verbundene mögliche Kostenreduzierung des Systems. Darstellung der Arbeitsschritte und der angewandten Methoden: Nach dem ersten Technikums-Probebetrieb wurde eine Reihe von Optimierungsmaßnahmen durchgeführt: - der Umbau des Rohsickerwasserzulaufs, - die Verwendung von Soda statt Bicarbonat für die Ammoniumoxidation in Reaktor 2, - der Einsatz von Membrandosierpumpen mit integrierten Rückschlagventilen für die Zugabe von Soda und Essigsäure, - der Einbau von zusätzlichen Polyurethan-Festbetten zur Vergrößerung der Oberfläche für die Besiedlung mit Mikroorganismen, - die Einstellung des Sollwerts für Reaktor 4 auf einen pH-Wert von 6,5, - ein Update der SPS-Steuerung der Nanofiltration zur freien Programmierung der Spülzyklen, - der Einbau eines Absperrhahns vor den Nanofiltrations-Vorfilter - und die Trennung des Nanofiltrationsablaufs vom Reaktoren-Sammelablauf zur Behälterleerung. Es wurde sowohl Rohsickerwasser der MEAB-Deponie Schöneiche als auch Sickerwasserkonzentrat der Deponie Vorketzin behandelt. Fazit: Wegen der durchgeführten Optimierungsmaßnahmen ist es prinzipiell gelungen, das Schöneicher Rohsickerwasser gemäß Anhang 51 der Abwasserverordnung aufzureinigen. In Vorketzin wurde die organische Belastung über 70% und Stickstoff über 80% reduziert. Nach Rückgang der Calciumfracht sollte es zukünftig möglich sein, mit der Zweistufen-Biologie das Sickerwasserkonzentrat ausreichend zu reinigen, da organische Belastung und Stickstoffgehalt geringer als im Schöneicher Rohsickerwasser sind. Um das Verfahren als Stand der Technik, vor allem für die Behandlung von Sickerwasserkonzentraten, zu etablieren, müssten die Laborvorgaben mit den Erfahrungen des Technikumsbetriebs kombiniert und in einer weiteren Versuchsreihe unter optimierten Bedingungen verifiziert werden.

Impact of urbanisation on the allergenicity of birch pollen grains

Evidence is compelling for a positive correlation between urbanisation and increment of allergic sensitisation and diseases. The reason for this association is not clear to date. Some data point to a pro-allergic effect of anthropogenic factors on susceptible individuals. Data analysing the impact of environmental - natural and anthropogenic - factors on the allergenicity of allergen carriers such as pollen grains are scarce, and if applicable only taken from in vitro experimental designs. This study will analyse one of the most common allergy inducers in northern Europe - the birch pollen. Under natural exposure conditions, birch pollen will be analysed with respect to their allergenicity. Within an interdisciplinary research team this study will evaluate the effect of natural (e.g. soil, climate, genetic background) and anthropogenic (e.g. traffic pollutants) factors on birch pollen in a holistic approach including analysis of allergen bioavailability, release of pollen associated lipid mediators from birch pollen grains, in vitro immunostimulatory activity and in vivo allergenic potential. These data collected in the time course of three years will significantly add to our understanding how urbanisation and climate change influence the allergenicity of birch pollen and will help us in the future to set up primary prevention studies.

Forschergruppe (FOR) 861: Cross-scale Monitoring: Biodiversity and Ecosystem Functions, Quantification of functional hydro-biogeochemical indicators in Ecuadorian ecosystems and their reaction on global change

Water is an intrinsic component of ecosystems acting as a key agent of lateral transport for particulate and dissolved nutrients, forcing energy transfers, triggering erosion, and driving biodiversity patterns. Given the drastic impact of land use and climate change on any of these components and the vulnerability of Ecuadorian ecosystems with regard to this global change, indicators are required that not merely describe the structural condition of ecosystems, but rather capture the functional relations and processes. This project aims at investigating a set of such functional indicators from the fields of hydrology and biogeochemistry. In particular we will investigate (1) flow regime and timing, (2) nutrient cycling and flux rates, and (3) sediment fluxes as likely indicators. For assessing flow regime and timing we will concentrate on studying stable water isotopes to estimate mean transit time distributions that are likely to be impacted by changes in rainfall patterns and land use. Hysteresis loops of nitrate concentrations and calculated flux rates will be used as functional indicators for nutrient fluxes, most likely to be altered by changes in temperature as well as by land use and management. Finally, sediment fluxes will be measured to indicate surface runoff contribution to total discharge, mainly influenced by intensity of rainfall as well as land use. Monitoring of (1) will be based on intensive sampling campaigns of stable water isotopes in stream water and precipitation, while for (2) and (3) we plan to install automatic, high temporal-resolution field analytical instruments. Based on the data obtained by this intensive, bust cost effective monitoring, we will develop the functional indicators. This also provides a solid database for process-based model development. Models that are able to simulate these indicators are needed to enable projections into the future and to investigate the resilience of Ecuadorian landscape to global change. For the intended model set up we will couple the Catchment Modeling Framework, the biogeochemical LandscapeDNDC model and semi-empirical models for aquatic diversity. Global change scenarios will then be analyzed to capture the likely reaction of functional indicators. Finally, we will contribute to the written guidelines for developing a comprehensive monitoring program for biodiversity and ecosystem functions. Right from the beginning we will cooperate with four SENESCYT companion projects and three local non-university partners to ensure that the developed monitoring program will be appreciated by locals and stakeholders. Monitoring and modelling will focus on all three research areas in the Páramo (Cajas National Park), the dry forest (Reserva Laipuna) and the tropical montane cloud forest (Reserva Biologica San Francisco).

Origin and fate of dissolved organic matter in the subsoil

Dissolved organic matter (DOM) is one major source of subsoil organic matter (OM). P5 aims at quantifying the impact of DOM input, transport, and transformation to the OC storage in the subsoil environment. The central hypotheses of this proposal are that in matric soil the increasing 14C age of organic carbon (OC) with soil depth is due to a cascade effect, thus, leading to old OC in young subsoil, whereas within preferential flowpaths sorptive stabilization is weak, and young and bioa-vailable DOM is translocated to the subsoil at high quantities. These hypotheses will be tested by a combination of DOC flux measurements with the comparative analysis of the composition and the turnover of DOM and mineral-associated OM. The work programme utilizes a DOM monitoring at the Grinderwald subsoil observatory, supplemented by defined experiments under field and labora-tory conditions, and laboratory DOM leaching experiments on soils of regional variability. A central aspect of the experiments is the link of a 13C-leaf litter labelling experiment to the 14C age of DOM and OM. With that P5 contributes to the grand goal of the research unit and addresses the general hypotheses that subsoil OM largely consists of displaced and old OM from overlying horizons, the sorption capacity of DOM and the pool size of mineral-associated OM are controlled by interaction with minerals, and that preferential flowpaths represent 'hot spots' of high substrate availability.

Schwerpunktprogramm (SPP) 1685: Ecosystem nutrition: forest strategies for limited phosphorus resources; Ökosystemernährung: Forststrategien zum Umgang mit limitierten Phosphor-Ressourcen, Microbial P mobilization and immobilization in the rhizosphere and root-free soil (SPP: P Nutrition & recycling)

Soil microorganisms can mobilize and immobilize phosphorus (P), and therefore strongly affect the availability of P to plants. In this project we hypothesize that the ratio of labile P to microbial P increases during the transition from acquiring to recycling ecosystems. Microbial and plant P uptake will be studied with 33P that will be quantified in microbial and plant biomass as well as in lipids. To what extent microorganisms immobilize and mobilize P during decomposition of soil organic matter will be explored with a 14C/33P labeled monoester. Seasonal dynamics of actual and potential P mineralization (33P dilution and phosphatase activity), and microbial P immobilization will be studied with soils of the transition from acquiring to recycling ecosystems. The contribution of litter-derived P will be explored in a litter exclusion experiment in the field. Spatial patterns of microbial and plant P mineralization in the rhizosphere will be explored by analyses of areas of high acid and alkaline (=microbial-derived) phosphatase activity by soil zymography, and their relations with areas of high rhizodeposition (14C imaging). In conclusion, we will analyse mechanisms of actual and potential microbial P mineralization and immobilization, localization, and consequences for P uptake by plants.

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